Bryan Research and Engineering, Inc.

- Technical Papers

Fuel Oil Compatibility Probed

J.W. HOLMES,
Bryan Research & Engineering, Inc.,
Bryan, Texas

J.A. BULLIN,
Texas A&M University,
College Station, Texas

ABSTRACT

A severe case of incompatibility occurred when three residual fuel oils were shipped as
a blend. The oils were blended as they were being loaded. During transport, a tar-like
precipitant formed, settled to the bottom and partially solidified. These fuel oils were
analyzed in an attempt to predict future potential incompatibility problems and to
investigate the known case of incompatibility.

Hydrocarbon Processing September 1983: 101-103.

Bryan Research & Engineering, Inc.

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A severe case of incompatibility occurred when three residual fuel oils were shipped as a blend. The oils were
blended as they were being loaded. During transport, a tar-like precipitant formed, settled to the bottom and
partially solidified. These fuel oils were analyzed in an attempt to predict future potential incompatibility problems
and to investigate the known case of incompatibility.

Several studies on the chemical and physical characteristics of heavy fuel oils and on handling problems have
been reported in the literature.1-18 An excellent summary of the handling problems has been presented by
Martin.19 As distinguished by Martin, "instability" refers to the tendency of a residual fuel to produce a deposit by
itself. "Incompatibility" is the tendency of a residual fuel to produce a deposit when blended with other fuel oils.
Two fuels, each stable in itself, may be incompatible when mixed. Although a case of incompatibility is easily
recognized after it has occurred, prediction of potential incompatibility is not so simple.

This study showed that major incompatibility problems occur when an oil with an asphaltene content greater than
three to five percent is blended with other oils which are primarily paraffinic. This improper blending caused the
precipitation of the tar-like material in the known case of incompatibility.

Better tests needed. Since the composition of these fuel oils is very complex, their characterization is generally
limited to meeting specifications as defined by the American Society for Testing and Materials (ASTM). These
usually include API gravity, viscosity, distillation temperature, and flash point. The composition of the heavy oil
depends on the origin of the crude as well as the refining scheme. These specifications are not indicative of the oil
composition. Since heavy fuel oils contain a very large number of different hydrocarbon compounds, their
composition is generally specified in terms of three main classes: paraffinic, aromatic and napthenic. The
aromatics can include some very heavy compounds in the molecular weight range of 1000 to 20,000, which are
known as asphaltenes.1 When fuel oils with a significant asphaltene content are mixed with oils of primarily
paraffinic content, the asphaltenes might precipitate.

Small amounts of asphaltenes commonly precipitate out of residual fuel oils during storage over periods of

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Bryan Research and Engineering, Inc. - Technical Papers

several months. The resulting sludge can often be remixed with the oil so the mixture is pumpable. However,
aromatic No. 6 oils, when sufficiently heated and aerated, will produce increasingly heavier asphaltenes until
transformed into tar or asphalt, usable in roofing and road surfacing.

In the present work, the results from an investigation of a severe case of incompatibility between heavy fuel oils
are presented. As a part of the investigation, samples of heavy fuel oil from several suppliers in the Gulf Coast
area were obtained and analyzed. The ASTM spot tests, the ASTM test for asphaltene content, gel permeation
chromatography (GPC) and other tests were used to evaluate the incompatibility of two or more fuel oils.

Analytical methods for this study. Samples of several heavy fuel oils and mixtures thereof were analyzed using
one or more of the following methods.

The only compatibility test listed in the ASTM Index of Tests is ASTM D2781 entitled "Compatibility of Fuel Oil
Blends by Spot Test." 20 The technical description states that this test is valid to predict the compatibility between
a residual fuel oil and a specific distillate fuel oil, such as a No. 1 or No. 2 fuel oil. In the test, equal volumes of the
two oils are blended at 140 to 145oF and a drop of the blend is allowed to spread on chromatographic paper of a
specified grade. The compatibility of the two oils is rated by comparing the spot to a series of reference spots.

A telephone survey of several heavy fuel oil suppliers in the Gulf Coast area revealed that this test is the only test
commonly used for compatibility of two or more heavy fuel oils. This test is used even though the method
specifically states that it is for a residual fuel oil and a specified distillate fuel oil.

Another test related to heavy fuel oils is ASTM D3279 for the determination of weight percent asphaltenes.21 In
this method, a sample is dispersed in n-heptane by gentle refluxing. The mixture is cooled and filtered. The
insoluble material is washed, dried and weighted to determine the weight percent of n-heptane insolubles. These
are called asphaltenes. The method is tedious and requires several hours to perform. In addition, only one gram
of sample is used and since the precipitated asphaltenes are transferred from a flask to a filter, several errors can
enter into the analysis.

A gel permeation chromatograph (GPC) was also used to analyze the heavy fuel oils. The GPC separates
molecules on the basis of linear molecular size and the samples elute in decreasing order of molecular length.
The samples were prepared by dissolving the oil in tetrahydrofuran and filtering. A Waters Associate Model
ALG/GPC 202 liquid chromatograph equipped with a Model R401 refractometer was used. Straight chain alkanes
from Applied Science and polystyrene standards from Waters Associates were used for the molecular size
calibration of the GPC. A detailed discussion of the application of GPC for the analysis of heavy fuel oils has been
presented by Philip, et al.22 They showed that the asphaltenic, paraffinic and light aromatic content of heavy fuel
oils can be easily determined by GPC. A chromatogram showing the molecular sizes and relative amounts of
each hydrocarbon group is presented in Figure 1.

Selected samples of different fuel oils were also mixed with varying amounts of n-heptane at room temperature.
These mixtures were visually inspected for precipitants. The ASTM spot test was also performed on some of
these mixtures.

Samples tested. The fuel oil samples used in the present work are identified as samples A through E. Sample F
is a portion of the solidified material resulting from an incompatible mixture of samples A, B and C.

Table I. Characterization of heavy fuel oils by ASTM D3279 and GPC

Sample Asphaltenes Asphaltenes Paraffins Light Aromatics
I.D. by ASTM by GPC by GPC by GPC
A 17 14 39 47
B 0 NIL 84 16
C 0 NIL 60 40
D 0 NIL 82 18
E 0 NIL 60 40
F 42 36 45 19

The results from the asphaltene tests by ASTM D3279 are shown in Table I along with some of the results from

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the GPC analyses. From the five oils from suppliers represented by samples A through E, the only one with any
appreciable asphaltene content was oil A. The GPC can also be used to estimate the asphaltene content of fuel
oils. As can be seen in Table I, the GPC results agreed closely with the asphaltene content by ASTM D3279.

A GPC chromatogram for oils A and C are presented in Figures 1 and 2, respectively. As determined by Philip, et
al22, the asphaltenes in oil A are the hydrocarbons with a molecular weight above about 2,900. This corresponds
to compounds with linear molecular sizes greater than n-C44H80. The paraffins are primarily those compounds
with linear molecular sizes between n-C44H80 and C12H26 while the light aromatics are those compounds with
linear molecular sizes smaller than n-C12H26. The estimated paraffinic and light aromatic content of oils are
included in Table l.

Figure 1. GPC chromatogram, Sample A.

Figure 2. GPC chromatogram, Sample C.

The GPC gives both leading and trailing tails to the peaks. Thus, when determining the asphaltene content, a
definite peak should exist in the molecular weight range above 2,900. In Figure 2, a slight leading tail above 2,900
molecular weight can be seen. However, no indication of a peak is evident and the oil contained no asphaltenes
as verified by ASTM D3279. If there were any doubt about the asphaltene content, the ASTM test could be
performed even though it requires several hours compared to about 30 minutes for the GPC analysis.

Previous blending of one of the fuel oils (sample A) is indicated by the GPC analysis. The GPC chromatogram
for oils B, C, D and E showed a smooth curve with hydrocarbon molecular weights primarily in the paraffin range.
The chromatogram shown in Figure 2 for oil C is representative for oils B, D and E. This can be contrasted to the
chromatogram for oil A in Figure 1, which shows major peaks in the asphaltenic, paraffinic and light aromatic
areas. The large light aromatic content suggests that light aromatics were added to the fuel oil to dissolve the
asphaltenes, to keep them in solution and to ensure that the oil would meet the specifications for No. 6 fuel oil. If
oil A is kept segregated, the light aromatics should keep the asphaltenes in solution and few problems should
occur. However, when oil A is blended with other oils of high paraffinic content, such as oils B through E, the
asphaltenes can be precipitated. The only difference between the precipitation caused by these paraffins and by
n-heptane used in ASTM D3279 is that lighter paraffins will precipitate more of the asphaltenes.

Another related series of tests consisted of mixing varying proportions of the fuel oil samples and n-heptane at

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room conditions. As expected, since no asphaltenes were present, oils B through E mixed readily with the n-
heptane in all proportions and caused no problems. However, when n-heptane was mixed with oil A which
contained about 15% asphaltenes, a fine brown precipitant formed at heptane/oil A ratios up to about 1.7:1. This
fine precipitant dispersed easily into the oil and probably would not have caused any pumping problems.
However, at heptane/oil A ratios near 2:1, a tar-like substance was formed almost immediately in the mixture. The
amount of the tar-like substance was about 5 to 10% of the mixture volume. Combined with the fact that no
previous asphaltene deposit had occurred in various blends of oils A, B and C, the heptane/oil blending tests
indicate that rather precise mixtures of the oils would be required to produce the tar-like deposit. These tests are
summarized in Table II.

Table II. Effect of blending fuel oils

Blends Observations
Severe incompatibility. Tar-like precipitant (Sample F) settled and partially solidified
A -- B -- C
during shipping.
A -- B
A -- C
Severe incompatibility possible
A -- D
A -- E
Fine brown precipitant formed at ratios up to about 1.7:1 for heptane/oil. Precipitant
dispersed easily. No pumping problems anticipated. At ratios near 2:1 heptane/oil,
n-heptane -- A
tar-like substance formed that was about 5% to 10% of the mix, although no change
was exhibited by the spot test.
n-heptane -- B
n-heptane -- C
No precipitant. Blends mixed readily in all proportions.
n-heptane -- D
n-heptane -- E

The spot test for compatibility. (ASTM D2781) was performed on some of the heptane/oil mixtures. The
heptane did not influence the spot rating of 1 for oils B through E. In the heptane/oil A mixture of about 2:1 where
the tar-like substance was formed, a spot rating of 1 was also obtained. This was apparently because the tar-like
deposit formed very quickly and any incompatibility in the remaining liquid was eliminated by the deposit. Thus,
the ASTM D2781 spot test may be helpful in predicting light asphaltene precipitation which might cause clogging
of fuel burners and perhaps deposit or sediment over several months of storage, but it is not a reliable tool to
predict major asphaltene deposits in blends of heavy fuel oils.

When blends of different fuel oils are needed, laboratory blends in the proper proportions could be made for visual
inspection of incompatibility. However, since most of the heavy fuel oils are black, visual observations through the
fluid are impossible. Close inspection with a stirring rod or spatula would reveal major deposits but could easily
miss minor or nonagglomerating deposits.

In summary. Gel permeation chromatography (GPC) can be used to characterize heavy fuel oils into asphaltenic,
paraffinic and light aromatic groups. The asphaltenic content by GPC and ASTM D3279 were found to agree
within about 15%. The GPC results can give an indication of previous blending of a fuel oil. The heptane/fuel oil
blends showed that if asphaltenes are present in a fuel oil, a fine precipitant can be formed and, at certain
heptane/oil ratios, a tar-like deposit can be formed. The ASTM spot test for compatibility, designed for blending a
light distillate oil with a heavy fuel oil, was found unreliable as a test for compatibility of two or more heavy fuel
oils.

ACKNOWLEDGMENTS

Special thanks are extended to Drs. C. V. Philip, R. G. Anthony and L. E. Mohrman of the Chemical Engineering
Department at Texas A&M University for their contributions to the work. The financial support of the Texas
Engineering Experiment Station and the Center for Energy and Mineral Resources at Texas A&M University is
very much appreciated.

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LITERATURE CITED

1. Long, R. B., "The Concept of Asphaltenes," ACS Symposium Series, Chemistry of Asphaltenes, Vol. 24, No. 4,
1979.

2. Ancillotti, F., Pescarello, E., "Fuel Blends Create Solubility Problems," Hydrocarbon Proc., 11, pp.295-299,
1977.

3. Dieker, E. V., "Two Years Experience in Handling and Burning No. 6 Low Sulfur Fuel Oil," Combustion, 1,
pp.34-36, 1972.

4. Exley, L. M., "A Practical Review of Residual Oil Firing Problems and Solutions," Cormbustion, 3, pp.16-23,
1970.

5. Harbert, W. D., "Jug Gives Online Bottom Blends," Hydrocarbon Proc., 58, pp.139-140, 1979.

6. Kneeper, J. I., Hutton, R. P., "Blend for Lower Pour Point," Hydrocarbon Proc., 9, pp.129-136, 1975.

7. Kyriacopoulos, G. B., "Blending Oil for Viscosity Index," Hydrocarbon Proc., 9, pp.137-138, 1975.

8. Robertson, W. N., "Fuel Oil Handling Systems for Glass Furnaces," Ceramic Bulletin, 57, pp.1,028-1,031,
1978.

9. Siegert, L. D., "Residual Oil Handling and Burning for Modern Cement Kilns," Rock Products, July, p. 72, 1971.

10. Yen, T. F., "Structural Difference Between Petroleum and Coal-Derived Asphaltenes," ACS Symposium
Series, Chemistry of Asphaltenes, Vol. 24, No. 4, 1979.

11. Speight, J. G. and W. E. Moschopedis, "Some Observations on the Molecular Nature of Petroleum
Asphaltenes," ACS Symposium Series, Chemistry of Asphaltenes, Vol. 24, No. 4, 1979.

12. Hall, G. and S. P. Herron, "Size Characterization of Petroleum Asphaltenes and Maltenes," ACS Symposium
Series, Chemistry of Asphaltenes, Vol. 24, No. 4, 1979.

13. Hernandez, J. O. and E. Choren, "Thermal Stability of Asphaltenes," ACS Symposium Series, Chemistry of
Asphaltenes, Vol. 24, No. 4, 1979.

14. Fuel Oil Manual, P. F. Schmidt, Industrial Press, New York, N.Y., 1951.

15. McKay, J. F., P.J. Amend, P. M. Harnsberger, T. E. Cogswell and D. R. Lathem, "Separation and Analyses of
Petroleum Residues," Laramie Energy Research Center, Energy Research and Development Administration,
Laramie, Wyo., pp.52-57.

16. "How to Deal with Heavy Fuel Residues," Chemicals, September 1979.

17. Petroleum Refinery Handbook, 4th ed., W. L. Nelson, McGraw-Hill Books, New York, N.Y., 1958.

18. Petroleum Products Handbook, 1st ed., V. B. Guthrie, ed., McGraw-Hill Books, New York, N.Y., 1960.

19. Martin, C. W. G., "The Stability and Compatibility of Fuel Oils," Proceedings Third World Petroleum Congress,
Section VII, pp.66-75.

20. American Society for Testing and Materials, Test Method ANSI/ASTM D2781.

21. American Society for Testing and Materials, Test Method ANSI/ASTM D3279.

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22. Philip, C. V., J. A. Bullin and R. G. Anthony, "Separation of Heavy Fuel Oils by Gel Permeation
Chromatography," submitted for publication in Fuel Processing Technology, June 1983.

copyright 2001 Bryan Research & Engineering, Inc.

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